CN1097036C - Gypsum-contg. composition and its use - Google Patents

Gypsum-contg. composition and its use Download PDF

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Publication number
CN1097036C
CN1097036C CN96196130A CN96196130A CN1097036C CN 1097036 C CN1097036 C CN 1097036C CN 96196130 A CN96196130 A CN 96196130A CN 96196130 A CN96196130 A CN 96196130A CN 1097036 C CN1097036 C CN 1097036C
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acid
fatty
group
cpd
gypsum
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CN1192725A (en
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蒂尔温·莱普休斯
约翰·克莱因
沃尔夫冈·克劳克
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/34—Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/08—Fats; Fatty oils; Ester type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C04B24/085—Higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Medicinal Preparation (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Cosmetics (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A gypsum-containing composition is characterised in that it contains 0.1 to 30% of a special fatty chemical additive and the use of said compositions to produce gypsum products, plaster facing, plaster floor, knifing fillers, mounting glues and modelling masses.

Description

Contain gypsum compositions and its purposes
The gypsum base composition and this composition that the present invention relates to contain specific oil chemical additive are used to produce gypsum member and specific building plaster, the purposes of gypsum plaster and mortar compound.
For a long time, dehydrated gyp-and semi-hydrated gypsum can be with water cure as useful raw materials because of it, and this raw material has many favourable characteristics, for example shrink for a short time, have resistivity against fire and have pH neutral when solidifying.A large amount of gypsum is to be produced by waste-gas desulfurization now, is subjected to environmental limit in use.
But, the gypsum lime mortar that solidifies, the water tolerance that a shortcoming of scraping slurry and coating is this system is lower.Still there is open question in outside use gypsum when for example using as mortar.
It is known that the specific polysiloxane of 2% (weight) can make gypsum have hydrophobicity by adding nearly.But when it was made, thus, its deficiency was to add polysiloxane with the serious harm environment, because polysiloxane can not biological degradation and unfavorable to the eubiosis.In addition, this modified gypsum can't reach the quality of externally using.
German patent DE-OS3238390 discloses a kind of mortar that gives system, and this mortar contains gypsum or cement as jelling agent, also contain in addition the 0.5-1% (volume) that gives the system mortar by 60-88%C 10-20Alkane mixture and/or glyceryl ester, the surfactant mixtures of higher fatty acid or fat and 12-40% is as emulsifying agent.Described mixture has hydrophobicity, causes mortar to have thermal insulation and frost resistance preferably.
JP-A-82/61648 discloses the gypsum dispersion agent, and they contain the condenses of (alkyl) naphthene sulfonic acid and formaldehyde, SiO 2 powder and randomly a kind of mineral oil that is selected from, the oil of ucon oil and natural oil.Gypsum fully is dispersed in the water, up to reacting with water and solidifying.From the mixture of gypsum and water is that isolated water reduces in process of setting the gypsum suspension, thereby obtains high-quality curing gypsum.
JP-A-73/73427 discloses resistivity against fire and the water-repellancy gypsum lime mortar wall that contains ether of cellulose, they are in the presence of the higher fatty acid metal-salt, with the suspension and the aqueous cellulosic resin of calcined gypsum, asbestos or glass fibre react in mould and heat with discharge water wherein and prepare.
JP-A-79/10974 discloses has the building slab that improves water-repellancy, and they are by for example adding a kind of higher fatty acid in cement or the calcined gypsum to hydraulic material or their salt prepares.
Belgian patent application 873812 discloses a kind of solidified plaster concrete, and it obtains by thorough mixing gypsum and water, and part gypsum wherein is by the metal-salt replacement of the lipid acid of indissoluble basically.Stearic acid, oleic acid, palmitinic acid or similarly sour calcium, aluminium, barium, lead, magnesium, zinc, copper or nickel salt can be used as hydrophobizing agent.
JP-A-82/3751 discloses waterproof, the plaster mould goods that solidify, and they are by hydrophobizing agent and calcium oxide semihydrate being reacted, add entry, molded and heating and obtain under carbonated atmosphere.This hydrophobizing agent is with higher fatty acid stearic acid for example, palmitinic acid, and oleic acid, coco-nut oil fatty acids etc. and their basic metal/alkaline-earth metal salt form, its consumption are 0.5-12% (weight).
JP-A-83/41750 discloses a kind of material that is used for plane institution movement; they are by making for example cement of hydraulic material; a kind of mixture, the material asbestos for example that contain inorganic fibre by cement, grain slag and gypsum etc.; glass fibre etc., the tackify material is methylcellulose gum for example, polyoxyethylene glycol etc.; with the metal-salt of higher fatty acid sodium stearate for example; potassium stearate, sodium oleate, potassium oleate etc. react and obtain.
JP-A-83/36955 discloses a kind of mortar material, and wherein the well-proportioned granulated blast-furnace slag of functional quality is as aggregate.Described mixture contains the granulated blast-furnace slag of the calcium sulfate monohydrate of 10 parts of weight and 50-200 part weight as aggregate, 0.03-3 part weight percent phosphoric acid salt, the protein-based retarding agent of 0.03-3 part weight and add soap in case of necessity in addition.
JP-A-82/175764 discloses a kind of water proof building member of inorganic materials, this member for example is to join by the aluminum saline solution with lipid acid to contain hydraulicity inorganic materials for example cement or gypsum, in the suspension of filamentary material and aggregate, join mixture in the mould and it is solidified, carrying out drying by thermal treatment then is more than 80 ℃ up to internal temperature.The aluminium salt that adds lipid acid is overheated in order to prevent, also in order to prevent to rupture and the peeling off of layer.
By EP-A-321816 as can be known the HLB value be the C of the ethoxylation of 4.5-11 12-22Fatty Alcohol(C12-C14 and C12-C18) can be used as surface active agent composition and joins in the gypsum base composition, can randomly add the methylcellulose gum of hydroxy alkylated in the said composition.Zhi Bei composition can be used as mortar and filler etc. thus.The purpose of adding ethoxylized fatty alcohol is to form caking in order to prevent when described composition mixes with water.
At " Con Chem Journal " the 2nd volume (1994), a kind of gypsum additives that contains the fatty alcohol radical of at least 10 carbon atoms is disclosed in the 23rd page.
JP-A-90/296780 discloses a kind of use C 10-16The sulfonate of fatty acid alkyl ester makes gypsum suspension foaming and the low density gypsum product made as whipping agent.
EP-A-54175 discloses a kind of based on cement, gypsum, and/or calcium hydroxide, the mortar mix of common fillers and assistant agent, the wherein ethylene oxide adduct of adding 0.05-0.5% water-soluble non-ionic cellulose ether and 0.01-0.05% Fatty Alcohol(C12-C14 and C12-C18) and/or lipid acid or its acid amides in anhydrous mortar mix.These mortar mix are used for the mortar of production aerating, gypsum and containing in the gluing mortar of calcium hydroxide, and for example being used for tiling and pattern structure and being used for the mortar jelling agent is the ordinary Portland cement of the aerating of base.
DE2908271 discloses and has used water based wax thereafter, paraffin and pitch dispersant coating gypsum plaster plate.
Task of the present invention provides a kind of gypsum base composition, and the mixture that uses specific oil chemical additive or various additives is to improve gypsum characteristics.Improved properties particularly comprises hydrophobicity, the control of setting time, rheological, water retention capacity and elastification.
Described task is solved by the feature of claim 1.
Therefore, the present invention relates to the gypsum base composition, it is characterized in that, by the dry mixture total amount, contain the additive of at least a oil chemistry of 0.1-30% (weight), additive is selected from following compound:
--at least a molecular weight is 143-20000 and the fatty cpd that contains at least one carboxyl and at least 8 carbon atoms, and/or their salt;
--at least a molecular weight is 130-20000's and contain at least one hydroxyl and have the fatty cpd of 8 carbon atoms at least;
--at least a molecular weight is 158-20000's and contain the fatty cpd of at least one ester group, and its acid constituents and/or alkoxide component contain 8 carbon atoms at least;
--at least a, molecular weight is 144-20000's and contain the fatty cpd of at least one ether, and wherein at least one group in two ethers contains at least 8 carbon atoms;
--at least a molecular weight is 129-20000 and contains at least one fatty cpd amino or at least one quaternary ammonium salt, wherein is arranged at least 8 carbon atoms of at least one group in around the nitrogen-atoms three or four bases;
--at least a molecular weight is 157-20000 and the fatty cpd that contains at least one amide group, and wherein the acid moieties of acid amides has at least 8 carbon atoms;
--at least a molecular weight is 128-20000 and the fatty cpd that contains at least one epoxide group and at least 8 carbon atoms;
--at least a molecular weight is 210-20000 and contains at least one anhydride group and the fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight is 193-20000 and the organophosphorus that contains at least 8 carbon atoms fat compound;
--at least a molecular weight is 174-20000 and the organic boron fatty cpd that contains at least 8 carbon atoms;
--at least a molecular weight is 164-20000 and the organosulfur fatty cpd that contains at least 8 carbon atoms;
--at least a molecular weight is 213-20000 and the fatty cpd that contains at least one urethane group and at least 8 carbon atoms, and/or
--at least a molecular weight is 130-20000 and contains at least one ketone groups and the fatty cpd that has 8 carbon atoms at least;
--its condition is not use higher fatty acid or its salt as at least a fatty cpd that contains at least one carboxyl separately, another condition is, do not use Fatty Alcohol(C12-C14 and C12-C18) or ethoxylized fatty alcohol as at least a fatty cpd that contains at least one hydroxyl separately, also having a condition is not use natural fat or oil as at least a fatty cpd that contains at least one ester group separately;
--another condition is not use C separately 10-16The sulphonate of fatty acid alkyl ester as organosulfur compound and
--its condition is not use the ethylene oxide adduct of fatty acid amide as at least a fatty cpd that contains at least one amide group separately.
The main ingredient of gypsum base composition of the present invention is dehydrated gyp-or semi-hydrated gypsum, comprises all based on the plaster of paris, the gypsum of the chemical modification of the gypsum that synthetic gypsum or waste-gas desulfurization produce (α-and β-semi-hydrated gypsum, anhydrous I, II, III gypsum).In principle, these are based on CaSO 4The various gypsum that solidify of the hydraulicity can exist with single form, also can exist with form of mixtures.
The used plaster of paris is normally in rotary kiln or the β type gypsum that obtains in the large-scale fluidizing furnace.Corresponding heterogeneous gypsum obtains by double-edged fine-toothed comb stove method, also obtains α type gypsum by autoclave simultaneously.
When using the gypsum of synthetic gypsum form, β type gypsum obtains to need not to carry out recrystallization by the Knauf rotary kiln by the large-scale fluidizing furnace of Knauf with by large-scale fluidizing furnace.Corresponding heterogeneous gypsum obtains by Knauf aggregate calcination method as synthetic gypsum, also obtains α type gypsum by the Giulini autoclave simultaneously.
But today, a large amount of gypsum was for example to pass through the Bischoff method by the desulfurization of waste gas, and SaarbergHolter method and short run organon produce.For example 200 ten thousand tons of waste gypsums have approximately been produced in nineteen ninety.The alpha-semi water plaster stone that is produced by VGDP gypsum (WGDP=waste-gas desulfurization factory) is significant in this respect.
In the gypsum base composition, count 50-99.9% (weight) by the inorganic gel agent component of dry mixture, preferred 70-98% (weight) as the consumption of the gypsum in the above-mentioned source of main products.
Fatty cpd of the present invention is by natural oil, especially lipid acid, Fatty Alcohol(C12-C14 and C12-C18) and their derivative or the by product of the acquisition of vegetables oil and animal oil.
In fact, they are that form with the natural mixture of various glycerin fatty acid esters exists, for example with plam oil, palm-kernel oil, palm stearines, sweet oil, rapeseed oil, Fructus Coriandri oil, Trisun Oil R 80, Oleum Gossypii semen, peanut oil, linseed oil, lard, fish oil, fish train oil (fish train oil) or Carnis Sus domestica fat.
The high natural content of saturated fatty acid according to them particularly preferably is Oleum Cocois, palm-kernel oil or butter.
Except these fats mixts, also can use corresponding single material.
Have 8-26 carbon atom, the example of the saturated fatty acid of preferred 12-22 carbon atom is a caproic acid, and is sad, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid ， docosoic, cerinic acid, pentadecylic acid, margaric acid, tridecanoic acid and Lignoceric acid.Have 8-26 carbon atom, the example of the unsaturated fatty acids of preferred 12-22 carbon atom is an Oleomyristic acid, Zoomeric acid, and oleic acid, elaidic acid, petroselinic acid, erucic acid, linolic acid, linolenic acid, arachidonic acid, tetradecanoic acid, Fish acid, docosahexenoic acid, timnodonic acid and cis 9-eicosenoic acid.
Have 8-26 carbon atom, the saturated fatty alcohol of preferred 12-22 carbon atom is that the example is a hexanol, octanol by reduction (hydrogenation) fatty acid methyl ester industry synthetic, nonyl alcohol, decyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, Stearyl alcohol, the pure and mild behenyl alcohol of 9-eicosylene.
Use by said structure unit deutero-and in gypsum, play the functionalized fatty cpd of corresponding institute requirement effect according to the present invention.Preferred use press molecular weight that GPC measures be greater than 129 to 20000 derivative or molecular weight greater than 1000 oligomeric fatty cpd and molecular weight greater than 2000 polymerized fatty compound.
Because these materials are a kind of mixture of complexity normally, so the important functional group that fatty cpd of the present invention has owing to itself has following feature.
In a preferred embodiment, oil chemical additive is at least a fatty cpd that contains carboxyl, and carboxyl is selected from the oxidation products of all Guerbet alcohols.Guerbet alcohol for example obtains (Soap.Cosm.Chem.Spec.53 (1987)) by own condensation Fatty Alcohol(C12-C14 and C12-C18) in the presence of alkali.Example comprises the 2-hexyldecanoic acid, 2-octyl group dodecylic acid, 2-decyl tetradecanoic acid, 2-dodecyl hexadecanoic acid, 2-tetradecyl octadecanoic acid, 2-hexadecyl arachic acid etc.Can choose the mixture that uses industrial Guerbet alcohol wantonly.
The other adduct of unsaturated fatty acids and dienophile is a vinylformic acid for example, toxilic acid, fumaric acid, acetylenedicarboxylic acid, vinylbenzene, the affixture of cyclopentadiene and alpha-olefins.
What other can be enumerated is the polymerized fatty acid that obtains by radical polymerization or thermal treatment.Described lipid acid also can pass through polymeric aliphatic ester, then ester hydrolysis group and obtaining.Example comprises dimerization and three polyglycerol fatty acids and the branched chain fatty acid that produces as the dimerization by product for example Unimac 5680 and different palmitinic acid.
Other suitable fatty acids is the lipid acid that obtains by the triglyceride level with oxidation that hydrolysis is blown.Example comprise by the blowing fish oil and the blowing rapeseed oil obtain.
At last, described definition also comprises the hexadecylenic acid as the by product of pyrolysis ricinolic acid methyl esters.
In first embodiment preferred, especially those also contain the compound of at least one hydroxyl to employed fatty cpd except containing at least one carboxyl.The example of this class comprises ricinolic acid.The 12-oxystearic acid and in synthetic nylon-11 as the 11-hydroxyl undecanoic acid of intermediate product, the reaction product of epoxidised fatty acid ester and water for example 9,10-dihydroxystearic acid or 9,10,12,13-tetrahydroxy-stearic acid.
In addition, except first kind fatty cpd, preferably use the oil chemical additive that except at least one carboxyl, also contains at least one hydroxyl.The example of this quasi-grease chemical additive is the partial ester that polycarboxylic acid or its acid anhydride and the fatty cpd that contains a plurality of hydroxyls form.The example of this class product comprises citric acid and C 8-26The partial ester of Fatty Alcohol(C12-C14 and C12-C18) or Viscotrol C, the half ester of toxilic acid and two polyalcohols or the half ester of Tetra hydro Phthalic anhydride and Viscotrol C.
That other is suitable is epoxidation C 8-100The reaction product of fatty acid ester and excessive polycarboxylic acid, for example reaction product of epoxidized soybean oil and hexanodioic acid.
At last also can use fatty cpd (for example Viscotrol C) and the α that contains ester and hydroxyl, beta-unsaturated acid is vinylformic acid for example, methylene-succinic acid, fumaric acid or the toxilic acid reaction product under the situation that adopts free-radical initiator.
In another preferred embodiment, first kind fatty cpd is by containing at least one carboxyl functional group, and the compound of at least one hydroxy functional group and at least one ether group is formed.This class fatty cpd comprises the reaction product of epoxidized fatty acid ester and monohydroxy-alcohol or polyvalent alcohol, and ester group wherein is hydrolyzed subsequently.The example is hard ester acid of hydroxyl methoxyl group and the hard ester acid of hydroxy butoxy.
In another preferred embodiment, first kind fatty cpd contains at least one ester group and at least one carbonyl.This class fat examples for compounds is a for example vinylformic acid of unsaturated fatty acid ester and dienophile, toxilic acid, the adduct of fumaric acid and acetylenedicarboxylic acid and unsaturated C 8-26The adduct of lipid acid and corresponding esters.
The reaction product that maleinization fatty acid ester and monohydroxy-alcohol and higher alcohols form half ester also is suitable for.Product has oligomeric or aggregation features.
Also can use lipid acid, the carboxyl end group ester of polyvalent alcohol and polycarboxylic acid is referring to by Dr.P Oldring ﹠amp; " resin that is used for surface-coated " that G.Hayward edits (Resins for Surface Coatings), III volume, SITA technology (London), 1987, the 188 pages.Corresponding product also can then obtain with the polycarboxylic acid esterification by the transesterification of fatty acid ester and polyvalent alcohol.
At last, also can use the fatty cpd of hydroxyl and the ester of excessive polycarboxylic acid.
In first group of fatty cpd, another kind of material is those compounds that also contain at least one ester group and at least one ether except at least one carboxyl.This class fat examples for compounds is the open-loop products of epoxidized fatty acid ester and monohydroxy-alcohol and polyvalent alcohol, then the carboxyl end group polyester that gets with the polycarboxylic acid reaction of molar excess.The epoxidation rapeseed oil of methyl alcohol open loop and the reaction product of Tetra hydro Phthalic anhydride are above-mentioned this class fat examples for compounds.
Another group fatty cpd that belongs to the first kind comprises the fatty cpd that also contains at least one ester group and at least one anhydride group except at least one carboxyl.Fatty acid ester and part belong to this other group of first kind fatty cpd with the affixture of the maleic anhydride of water or monohydroxy-alcohol or polyol reaction.The example that can mention is the partial reaction product of maleinization soya-bean oil and butanols.
Other group fatty cpd that belongs to the first kind is those compounds that also contain at least one acid anhydride base except at least one carboxyl.Described other little compounds comprises the reaction product of unsaturated fatty acids and maleic anhydride.Reaction can be carried out under the condition of heat treated or freeization (radikalisch).The example of this group comprises the linolenic acid of maleinization and the oleic acid of maleinization.According to the present invention, the second quasi-grease chemical additive comprises the fatty cpd that contains at least one hydroxyl.They are that Guerbet reaction by the pure and mild unsaturated fatty alcohol of saturated fatty obtains.The example of this class Guerbet alcohol is a 2-hexyl decyl alcohol, the 2-Standamul G, and 2-decyl tetradecanol, 2-dodecyl cetyl alcohol, 2-tetradecyl Stearyl alcohol, 2-hexadecyl eicosanol is selected from the Guerbet alcohol of erucyl alcohol ， behenyl alcohol and oleyl alcohol.Randomly can use the mixture that Guerbet reaction produced by industrial Fatty Alcohol(C12-C14 and C12-C18).
The fatty cpd that contains a plurality of hydroxyls for example comprises ricinoleyl alcohol, and 12-hydroxyl Stearyl alcohol has the dimer diol and the trimerization triol (hydrogenated products of dimerization and trimerization fatty acid ester) of 18-52 carbon atom.
In a preferred embodiment, the second quasi-grease chemical additive can contain at least one hydroxyl and at least one ester group.This quasi-grease chemical additive that belongs to second class is a Viscotrol C, and the Viscotrol C of partial dehydration is with monocarboxylic acid and the partially acylated Viscotrol C of polycarboxylic acid, the polyester of ricinolic acid and 12-oxystearic acid (Estolids); The reaction product of epoxidised fatty cpd and monocarboxylic acid and polycarboxylic acid or monohydroxy-alcohol and polyvalent alcohol; The transesterification products of fatty acid ester and polyvalent alcohol (partial glyceride); Viscotrol C and other triglyceride level be rapeseed oil for example, the transesterification products of Trisun Oil R 80 under alkaline randomization condition; Fatty Alcohol(C12-C14 and C12-C18) and hydroxycarboxylic acid be tartrate for example, citric acid, the ester of gluconic acid reaction.These products also can be by being similar to lipid acid, and the Synolac of monohydroxy-alcohol and polyvalent alcohol and polycarboxylic acid is synthetic, forms the oligopolymer of terminal hydroxy group and obtain.Corresponding product can also be by polyvalent alcohol the transesterification of fatty acid ester, then carry out esterification and prepare with polycarboxylic acid.Other representative example is the partial ester Rylo MG 19 for example of lipid acid and polyvalent alcohol, three methyl alcohol propyl group SUNSOFT Q-182S, five monolaurins, sorbitan one coconut palm acid esters.The product that contains the terminal hydroxy group esterification of hydroxy aliphatic compound and polycarboxylic acid.
Other group of second class comprises the fatty cpd that also contains at least one amido or corresponding quaternary ammonium salt except at least one hydroxyl and at least one ester group.The example of these fatty cpds is reactions of epoxidised fatty acid ester and unit and polyamine, and ester functional group does not have amidated product.The example of this class reaction product is the reaction product of methyl epoxy stearate and 1, uses ammonia, and unit and polyamine amidation fatty acid ester, especially triglyceride level, and deglycerizin not randomly carry out the part amidation.
In another preferred group of second class, fatty cpd not only contains at least one hydroxyl, but also contains at least one ester group and at least one amide group.This product is by using ammonia, unit and polyamine amidation fatty acid ester, especially triglyceride level, and the alkoxide component of not removing in the ester (glycerine) obtains.An example of this class product is rapeseed oil and the reaction product that is lower than normal hard esteramides.
In the preferred group of the preferred fatty cpd of another second class, fatty cpd can also contain at least one ester group and at least one acid anhydride base except at least one hydroxyl.This class fat examples for compounds be the hydroxyl fatty acid ester for example Viscotrol C and maleic anhydride in the catalyzer that free-radical initiator is arranged ditertiary butyl peroxide for example, AIBN, the reaction product under the existence of tert-butyl hydroperoxide and dibenzoyl peroxide.
In the preferred group of another preferred second class, oil chemical additive can also contain at least one ether except at least one hydroxyl.This compounds is to become oligomeric terminal hydroxy group polyethers by the etherificate of the fatty cpd that contains a plurality of hydroxyls (for example ricinoleyl alcohol, 12-hydroxyl Stearyl alcohol, dimer diol, trimerization triol) (for example by adopting an acidic catalyst dehydration) to obtain.The product of this class fatty cpd has been described among the DE4316245 (A1).
In the preferred group of the preferred fatty cpd of another second class, comprise that those also contain the fatty cpd of at least one amide group except at least one hydroxyl.These fatty cpds are fatty cpd and the ammonia that contains carboxyl and hydroxyl, the reaction product of unit and polyamine.Example comprises the Viscotrol C acid amides, 12-oxystearic acid quadrol, hydroxyl-methoxyl group stearic acid decoylamide, dihydroxystearic acid butyramide.Above-mentioned fatty cpd also is for example reaction product of coconut fatty acid single ethanol amide and Stearic acid diethanolamine salt of carboxylic fatty cpd and oxyamine.
In the 3rd embodiment preferred of the present invention, fatty cpd contains at least one ester group.This fatty cpd is Acrawax three methyl alcohol propyl group trioleates for example especially, rapeseed oil fatty acid methyl esters, tricaprylin and oleic acid-2-(ethyl hexyl) ester.The fatty cpd of the above-mentioned type also has for example vinylformic acid of fatty acid ester and dienophile (dieneophiles), toxilic acid, fumaric acid, ethynyl dicarboxylic ester, vinylbenzene, the reaction product of cyclopentadiene etc.Reaction also can be passed through heat treated, the carrying out with photochemical treatment of radical.
Other fatty cpd that is included in the 3rd preferred embodiment of the present invention is the oil ﹠ fat of blowing; the fat of radical polymerization; Toenol 1140-stand oil, the rapeseed oil of the thermopolymerization of Tuo Shui Viscotrol C and consequent stand oil and with the complete acetylated castor oil of monocarboxylic acid fully.
At last, the ester that obtains of Fatty Alcohol(C12-C14 and C12-C18) and monocarboxylic acid and polycarboxylic acid reaction also is suitable for.The fatty cpd that contains carboxyl also can be used for using the Fatty Alcohol(C12-C14 and C12-C18) esterification.Example comprises the oil base oleic acid ester, distearyl adipic acid ester, oil base acetic ester.
In the 3rd embodiment preferred of the present invention, fatty cpd also contains at least one epoxy group(ing) and at least one ether group except at least one ester group.This class fatty cpd comprises the epoxidized fatty acid ester with monohydroxy-alcohol or polyol moiety open loop, for example methyl epoxy stearate and the reaction product that is lower than its normal octanol.
In another preferred group of the 3rd embodiment preferred, fatty cpd also contains at least one amido except at least one ester group.This class fatty cpd comprises the tertiary amine ester that obtains of trolamine or 3-hydroxy-n-crassitude and the reaction of carboxylic fatty cpd for example that contains hydroxyl.Product can by with Mono Chloro Acetic Acid, methyl halide, methyl-sulfate etc. reaction and by quaternized, and be transformed into amphipathic compound thus.
Another group of preferred the 3rd class fatty cpd comprises the fatty cpd that also contains at least one epoxide group except at least one ester group.This class fatty cpd is part and complete epoxidised fatty acid ester, and the example of this class epoxidized fatty acid ester has: methyl epoxy stearate, epoxystearic acid-2-(ethyl hexyl) ester.Preferred glyceryl ester is for example soya-bean oil epoxide of triglyceride level, Toenol 1140 epoxide, rapeseed oil epoxide, epoxidised Trisun Oil R 80.
In another group of the 3rd class, fatty cpd of the present invention also contains at least one acid anhydride base except at least one ester group.This fatty cpd is to contain for example reaction product of maleic anhydride of the fatty acid ester of two keys and dienophile in its alcohol or acid constituents.
In the 4th embodiment preferred, fatty cpd of the present invention contains at least one ether, preferably has 8-26 carbon atom, more preferably the alkylether radicals of 12-22 carbon atom.This class ether obtains by known method, for example by Williamson ' s ether synthesis method or by with saturated, an acidic catalyst dehydration of unsaturated and branched fatty alcohol and acquisition.The example of this class aliphatic ether is a dicaprylyl ether, didecyl ether, distearyl ether and two mountain Yu ethers.
In the 5th embodiment preferred, oil chemical additive is at least one fatty cpd that contains at least one amine groups.These amine are the amidations by lipid acid, dehydration and reduction and obtain.The example of this class aliphatic amide comprises stearylamine and lauryl amine.Described amine also can by with Mono Chloro Acetic Acid, methyl halide, sulfuric acid dialkyl etc. reaction and quaternized.Example comprises stearyl trimethylammonium salt ammonium chloride, lauryl triethyl ammonium sulfate.
In a group of the 5th preferred embodiment, comprise the fatty cpd that except at least one amido, also contains at least one amide group.This class fat examples for compounds is the reaction product of epoxidised fatty acid ester and unit and polyamine, and wherein, ester functional group is simultaneously by amidation, and example comprises the reaction product of methyl epoxy stearate and stearic amine.
In the 6th embodiment preferred of the present invention, fatty cpd of the present invention contains at least one amide group.This class fatty cpd is fatty cpd and the ammonia that contains carboxyl, the reaction product of unit and polyamine.Example comprises stearic amide, amine hydroxybenzene, stearic acid quadrol.
In the 7th embodiment preferred, fatty cpd of the present invention contains at least one epoxide group.This class fatty cpd for example is the C that contains at least one two key 8-26The epoxidation product of alkylate, for example 1-epoxy octadecane.
In the 8th embodiment preferred, oil chemical additive is the fatty cpd that contains at least one anhydride group.This class fatty cpd is to obtain by the fatty cpd that the dehydration of employing acetyl acid anhydride contains one or more acid groups by currently known methods.This class fat examples for compounds is the distearyl acid anhydride, two oily acid anhydrides, dimerization fat acid anhydride.
In the 9th embodiment preferred, oil chemical additive of the present invention is the fatty cpd that contains at least one organophosphorus.This class fat examples for compounds is phosphoric acid and phosphorous acid and contain the ester of the fatty cpd of hydroxyl especially.Phosphoric acid and phosphorous acid and contain the acid amides of the fatty cpd of amido.
In the tenth embodiment preferred, oil chemical additive is the fatty cpd that contains organic boron.This class fat examples for compounds is boric acid and the ester that contains the fatty cpd of hydroxyl.Organic boron fatty cpd for example can be by obtaining with boric acid and Sodium Tetraborate reaction.
In the 11 embodiment preferred, oil chemical additive is the fatty cpd that contains at least one organosulfur.This class fat examples for compounds is sulfuric acid (vitriol) and sulfurous acid (sulphite) and the ester that contains the fatty cpd of hydroxyl.Other example is fatty cpd and the chlorsulfonic acid with active group (two keys, alpha-methylene group), and sulphur trioxide or oleum form the reaction product of sultone and sulfonic acid.The reaction product of unsaturated fatty acid ester and elementary sulfur and sulfur dichloride.Example comprises the sulfation rapeseed oil, the sulfonate of fatty acid ester, the sulfuric ester of Fatty Alcohol(C12-C14 and C12-C18), the reaction product of Toenol 1140 and sulphur (blowing ointment and white factice), Sulfated Viscotrol C (Turkey red oil).
In the 12 embodiment preferred, oil chemical additive is the fatty cpd that contains at least one urethane group.This class fatty cpd is by the fatty cpd that contains hydroxyl and unit and polybasic isocyanic ester are randomly reacted in the presence of general catalyzer, forms monomericly, oligomericly obtains with polymerized product.Example is the reaction product of Viscotrol C and two isocyanic acid benzhydryl esters, the reaction product of 1-octanol and methyl isocyanate.
In the 13 embodiment preferred, oil chemical additive is the fatty cpd that contains at least one ketone group group.This class fatty cpd be by epoxidised fatty acid ester and Lewis acid or lithium salts reset obtain or their derivative.Example is ketone group methyl stearate and 9-ketone group stearic acid.Corresponding ester can also obtain by the isomerization castor oil derivative.
Also can use the aliphatic ketone of the method for preparative organic chemistry by the lipid acid preparation; Example is to be higher than under 300 ℃ the temperature, and the pyrolysis fatty acid magnesium salt discharges CO 2And water (the open DE2553900 of Germany).Example is distearyl ketone (stearone) and Er behenone (behenone).
Described in the present invention monocarboxylic example is following compound: formic acid, acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid is sad, n-nonanoic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, palmitinic acid, margaric acid, stearic acid, nondecylic acid, eicosanoic acid docosoic, Lignoceric acid, cerinic acid and honeybeeization acid, phenylformic acid, the benzoic acid derivative that replaces, 4-hydroxy-benzoic acid, Tripon, 2 hydroxy propanoic acid, the 3-hydroxy-propionic acid, oxyacetic acid, Whitfield's ointment, chloro pentane acid, 4 hydroxybutyric acid, amygdalic acid, toluylic acid, gallate, styracin is by the resinous acid of pine resin and appropriate your resin abietic acid for example.
The example of described polycarboxylic acid is following compound in the present invention: oxalic acid, propanedioic acid, succsinic acid, pimelic acid, toxilic acid, fumaric acid, pentanedioic acid, hexanodioic acid, suberic acid, sebacic acid, 1,11-undecane diacid, 1,12-dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer (fatty acid) yl, three polyglycerol fatty acids, tartronic acid, oxysuccinic acid, acetylenedicarboxylic acid, tartrate, citric acid.
In the present invention, the example of monohydroxy-alcohol is following compound: methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, 2-Ethylhexyl Alcohol, sec-n-octyl alcohol, a phenylglycol, abietinol, polyoxyethylene glycol one alkyl oxide, hexalin.
Described in the present invention examples of polyhydric alcohols is following compound: 1,1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 2,3-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, Diethylene Glycol, new penta ethylene glycol, 1,4-pair-the hydroxymethyl hexanaphthene, the 2-methyl isophthalic acid, ammediol, 1,2, the 6-hexanetriol, glycerine, two glycerine, Polyglycerine, trihydroxymethyl propane, methyltrimethylolmethane, tetramethylolmethane, Sorbitol Powder, formic acid alcohol (formit), methyl glucoside, dimer diol, trimerization triol, glucose, alkyl polyglucoside, two saccharidess and many saccharidess.Above-mentioned all alcohol can use with the form of EO or PO affixture.Also comprise polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol, cyclohexyl glycol, EO/PO segmented copolymer (Pluronic and Pluriol_ type).
In the present invention, the example of unit amine is following compound: methylamine, dimethyl amine, ethylamine, butylamine, stearic amine, oil base amine, the derivative of amino-benzene or replacement, aminocyclohexane and tetramethyleneimine.
In the present invention, the example of polyamine is following compound: quadrol, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine, diethylenetriamine, Triethylenetetramine (TETA), 1, the 2-diamino-cyclohexane, 1,4-diamino-cyclohexane, 1,3-diamino-2,2-dimethylpropane, 2,5-diamino-2, the 5-dimethylhexane, 1,10-diamino decane, 1, the 4-diaminobutane, 12-diamino dodecane, the diamines of dimer (fatty acid) yl, 1,8-diamino octane, 1,8-diamino-right-methane, 1,5-diamino pentane, 1,3-diamino-2-propyl alcohol, 1,3-diamino diamantane, phenylenediamine, diaminobenzene.
The example of the oxyamine among the present invention is following compound: Monoethanolamine MEA BASF, diethanolamine, 1,6-hexanol amine, 2-Trans-4-Amino Cyclohexanol, 4-Trans-4-Amino Cyclohexanol, hydroxymethyl-pyrrolidine.
The example of the unit isocyanic ester among the present invention is following compound: the isocyanic acid phenylester, alkyl isocyanate, isocyanide ethyl acetoacetic acid ethyl ester, the compound that contains isocyanic ester that TI and the reaction by multifunctional especially two functional isocyanic ester and unit alcohol or amine obtain.
The example of polyfunctional isocyanate among the present invention is the following compound that on average contains 2-4 NCO group.The example of suitable isocyanic ester is a l,5 naphthylene diisocyanate, 4, and 4-methyl diphenylene diisocyanate (MDI), hydrogenant MDI (H 12MDI), xylyl vulcabond (XDI), tetramethyl xylene group diisocyanate (TMXDI); 4,4 '-phenylbenzene dimethylmethane vulcabond, dialkyl group diphenylmethanediisocyanate and tetraalkyl diphenylmethanediisocyanate; 4; 4 '-the dibenzyl vulcabond, 1, the 3-phenylene vulcabond; 1; the 4-phenylene vulcabond, the heteropolymer of toluenediisocyanate (TDI), randomly its mixture; 1-methyl-2; 4-two isocyanide acyl hexanaphthenes, 1,6 '-two isocyanide acyl-2; 2; the 4-trimethyl cyclohexane, 1,6-two isocyanide acyls-2; 4; the 4-trimethyl cyclohexane, 1 '-isocyanide acyl methyl-3 '-isocyanide acyl-1,5; 5 '-trimethyl-cyclohexane (IPDI); the vulcabond of chlorating and bromination, phosphorated vulcabond, 4; 4 '-two isocyanide acyl phenyl R 116s; tetramethoxy butyl-1,4-vulcabond, butyl-1; the 4-vulcabond; hexyl-1,6-vulcabond (HDI), dicyclohexyl methyl vulcabond; cyclohexyl-1; the 4-vulcabond, ethylidene diisocyanate, phthalic acid-two-isocyanide acyl diethyl acetamidomalonate; the polymeric polyisocyanate that contains reactive halogen atom; 1-chloromethyl phenyl-2 for example, 4-vulcabond, 1-2-bromomethylphenyl-2; the 6-vulcabond; 3,3-pair-chloro-4,4 '-diphenyl diisocyanate.The polymeric polyisocyanate of sulfur-bearing for example is by 2 moles hexamethylene diisocyanate and 1 mole thiodiglycol or the reaction of dihydroxyl dihexyl sulfide are obtained.Other important vulcabond is a trimethyl hexamethylene diisocyanate, 1, and 4-two isocyanide acyl butane, 1,12-two isocyanide acyl dodecane and dimer (fatty acid) yl diisocyanates.The hidden polymeric polyisocyanate of part that can form the urethane of self-crosslinking also is interesting, dimerization inferior cresyl vulcabond for example, or partially or completely for example with phenol, the trimethyl carbinol, phthalic imidine, the polymeric polyisocyanate of hexanolactam reaction.
Obviously, not only can use the mixture of the oil chemical additive that belongs to all kinds of, but also can use the mixture of any compound that belongs to indivedual classes.
Above-mentioned oil chemical additive can be by any means and gypsum, randomly mixes use in every way with other component.At first, so-called single component variant comprises and contains gypsum, the gypsum base composition of oil chemical additive and other assistant agent and additive.Therefore, the user only to need to wherein adding entry thereby this variant be preferred especially.Oil component can be mixed use with the gypsum powder physical property separately, also can mix use with other assistant agent and additive.But, also these components can be incorporated in the gypsum or be adsorbed by gypsum or under the temperature that is higher than room temperature (＞25 ℃), apply.
Perhaps, also can be before adding water, add behind the water or two component variants and oil chemical composition and other assistant agent and additive are being mixed gypsum on the spot with water blended place when adding water.
In preferred the 3rd embodiment of the present invention, the salt of the fatty cpd of carboxyl will be arranged, for example corresponding lipid acid and amine is the salt of Monoethanolamine MEA BASF for example, at room temperature adds and react under hydrolysis is analysed when producing plasterboard to generate corresponding amine.
At last, the invention still further relates to the above-mentioned oil chemical additive of use in dipping or coating ready-formed gypsum member or plasterboard.For this purpose, can directly apply oil chemical additive or even with the form of solution in solvent or in water the form with dispersion liquid or suspension apply.Available any mode commonly used applies, for example dip-coating, and spraying, roller coating is brushed etc.
The present invention also relates to a kind ofly contain following oil chemical additive in order to handle gypsum member and gypsum plaster material:
--at least a molecular weight is 143-20000's and contain at least one carboxyl and have the fatty cpd of 8 carbon atoms at least, and/or their salt;
--at least a molecular weight is 130-20000's and contain at least one hydroxyl and have the fatty cpd of 8 carbon atoms at least;
--at least a molecular weight is 158-20000's and contain the fatty cpd of at least one ester group, and its acid constituents and/or alkoxide component contain at least 8 carbon atoms;
--at least a, molecular weight is 144-20000's and contain the fatty cpd of at least one ether, and wherein at least one group in two ethers contains at least 8 carbon atoms;
--at least a molecular weight is 129-20000 and contains at least one fatty cpd amino or at least one quaternary ammonium salt, wherein, is arranged at least 8 carbon atoms of at least one group in around the nitrogen-atoms three or four bases;
--at least a, molecular weight is 157-20000 and the fatty cpd that contains at least one amide group, and wherein the acid moieties of acid amides contains at least 8 carbon atoms;
--at least a molecular weight is 128-20000 and contains at least one epoxide group and the fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight is 210-20000 and contains at least one anhydride group and the fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight is 193-20000 and contains the organophosphorus fat compound that has 8 carbon atoms at least;
--at least a molecular weight is 174-20000 and contains the organic boron fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight is 164-20000 and contains the organosulfur fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight is 213-20000 and contains at least one urethane group and have the fatty cpd of 8 carbon atoms at least, and/or
--at least a molecular weight is 130-20000 and contains at least one ketone groups and the fatty cpd that has 8 carbon atoms at least;
--its condition is not use the fatty cpd with at least 10 carbon atoms as at least a fatty cpd that contains at least one hydroxyl separately.
As mentioned above, containing the oil chemical additive of carboxyl, is the additive that belongs to the first kind, can directly use also and can use with their form of salt.The counter ion of carboxyl can be selected from mineral ion, for example monovalence or polyvalent metal ion, or ammonia and be selected from for example alkanolamine of corresponding organic bases, amine etc.
The preparation method of salt is identical with the preparation method of metallic soap, is prepared by acid and metal or amine compound under the strong alkaline condition in appropriateness.In many cases, also the oxide compound of available equimolar amount or oxyhydroxide prepare salt.The preparation of salt can also be carried out when preparation gypsum/water mixture on the spot.In addition, salt is changed, the soap class or the salt that are about to sodium are transformed into calcium salt or other salt.The salifiable processing method of shape is described in the technical chemistry macropaedia (Ullmann, Encyclopedia of TechnicalChemistry) of Liv Ullmann, and the 16th volume A, is entitled as in the summary article of " metallic soap class " (Metallic Soaps) by the 361st page.
Under the situation of the oil chemical additive that contains the fatty cpd with at least one amido, the preparation of corresponding salt can be carried out protonated carrying out by alkylation or with acid.When except at least one amido, also containing the oil chemical additive of at least one carboxyl, even can form inner salt.Because calcium sulfate hemihydrate and calcium sulfate dihydrate have certain dissolubility in water,, also can form salt subsequently with carboxyl so there is the free calcium ion to exist.
In addition, gypsum can also contain other metal ion, for example sodium, magnesium, potassium, strontium, lithium, rubidium, iron (II), barium, molybdenum (II), zinc, aluminium and manganese (II), these ions between the gypsum mixing period or even after gypsum solidifies, also can form salt with carboxy-functionalized fatty cpd, referring to the article among " epoch chemistry " (" Chemiein unserer Zeit "), the 19th volume (1985), the 137-143 page or leaf.Can for example carboxylic fatty cpd of the salifiable material of shape and alkali (Ca (OH) for example by adding 2, amine) during stirring gypsum simultaneously or form salt after a time.Under the situation that contains the amine fatty cpd, can add corresponding acid.
According to the present invention, other component that contains gypsum compositions is for example general filler, and assistant agent and additive change these components according to service requirements.These extraneous components are mineral filler and/or mineral filler clay for example especially, sand, stone, cement, slag, glass, silica gel, vitriol (for example calcium sulfate dihydrate), oxide compound (magnesium oxide for example, calcium oxide), glass and mineral fibre, synthon, cenosphere, lightweight organic filler (for example styrofoam) comes the particle (making with extra care) of self-circulation factory, the paper powder, wood chip and sawdust, cellulosic fibre etc.Other suitable additive is a sanitas, rust-preventive agent and dyestuff.
At coating, normally used siccative can be used as other component adding of gypsum base composition of the present invention in varnish and the printing ink.According to 55901 (in March, 1988), siccative is interpreted as the organic acid metal-salt, and they are soluble in organic solvent and tackiness agent and join in the drying products of oxidation to promote drying process.From the angle of chemistry, siccative belongs to the metallic soap class, and can be used as so-called siccative and exist with solid and dissolved form.But they also can be used in combination with emulsifying agent with the form of aqueous emulsifying.The example of acidic components is aliphatic carboxylic acids, as sad, or lipid acid, naphthoic acid or or even resinous acid.Corresponding cobalt salt, manganese salt or lead salt, but preferred cobalt salt and manganese salt can be used as main siccative, and it is directly used in the oxidising process that promotes fatty cpd.And zinc, iron, calcium, cerium, plumbous and barium salt can be used as the drying aid agent and use, and they itself do not have any katalysis, but can be used in combination synergistically with the above-mentioned siccative of mentioning.At last, zirconium and aluminium salt can be used as equal siccative.The example of commercially available siccative is product A dditol VXM 6206 and 4940, Solingen, and Cobalt 10, Toenol 1140 varnish, Nuodex Cerium 6 and Zinc 8, Alusec 591 and Nourydrier 973.But,, when use contains the fatty cpd of at least one carboxyl, then need not to use the above-mentioned salt of mentioning according to the present invention.In addition, the inorganic salt that can use above-mentioned metal are oxyhydroxide for example, so that form siccative on the spot.The consumption of siccative is generally 0.01-1% (weight) by oil chemical additive.
Other component of gypsum base composition of the present invention is to reduce the material with solidification of water requirement, and this class material is commonly called softening agent.The example is an alkyl aryl sulfonic acid ester, Sulfite lignin or melmac.For example at " cement, lime, gypsum ", the 21st rolls up the summary of relevant softening agent in the 415-419 page or leaf (1968).Plasticizer dosage is generally 0-10% by the total amount of the present composition.
The material that has a throwing out by interpolation for example in GB-A-1049184 disclosed polyethylene oxide can also increase water requirement.The add-on of these assistant agents is counted 0-10% (weight) by dry mixture.
Chemical substance by adding thickening for example Mierocrystalline cellulose and starch ethers can stabilize water/gypsum mixtures, to prevent deposition or to separate.These thickening materials almost cut little ice to water requirement.The amount that joins the thickening material in the dry mixture of the present invention is counted 0-5% (weight) by dry mixture.During churning, can also add polymer dispersion liquid in gypsum, this mainly is in order to improve elasticity and bounding force.
In addition, composition of the present invention can contain the assistant agent of promotor effect.Promotor especially can be selected from various mineral acids and their salt, more preferably is selected from sulfuric acid and vitriol.In this respect, calcium sulfate dihydrate occupies special position, and they have strong promoter action when being finely divided form, thereby are removed fully in the calcination process of raw material gypsum.The promoter action of this material is usually based on solubleness and the increase of dissolution rate and the improve of nucleation rate of calcined gypsum.
Other assistant agent of gypsum base composition of the present invention is known retarding agent, and they are to slow down to solidify and process of setting.They especially comprise institute's organic acid and its salt, and the organic colloid that forms as degraded product in for example proteinic hydrolysis of high molecular crude substance also comprises phosphoric acid salt and borate.Dextrin and Root of Shrubalthea also are suitable for.Retardance mechanism is variable.Prolonged inductive phase because of the nuclear toxicity of polymer colloid.The slowed down speed of growth of dissolution rate and two crystallines of semihydrate of other retarding agent.The retardation of dehydrated gyp-II does not have special practical significance usually, has to they are quickened very slowly and always because they have become the speed of dihydrate.This component shared percentage composition in gypsum compositions of the present invention is counted 0-5% (weight) by dry mixture.
Known as the professional, the consumption of water depends on the type of used gypsum raw material, required consumption when reaching free flowing mixture with even denseness, the water demand ratio pot of rotary kiln-β gypsum is fried the big of gypsum (kochergips), and the water requirement that pot is fried gypsum big than heterogeneous gypsum, the water requirement of heterogeneous gypsum is big than autoclave gypsum then.In addition, the consumption of water also has a significant effect to unit weight and the intensity that forms gypsum product.Need not to carry out any concrete measure, the unit weight of the gypsum product that obtains with little water processing α gypsum is big, the intensity height, thus avoided undesirable fragility in the building industry.For reaching free-pouring denseness, the water requirement of β gypsum and heterogeneous gypsum is bigger than α gypsum.Therefore, when using in whole building industry, prepared gypsum product has medium tenacity and higher elasticity when unit weight is low.For production lightweight or graphite product, for example can add hydrogen peroxide (producing oxygen) or diluted acid and carbonate and (produce CO 2).
The invention still further relates to the gypsum base composition of the above-mentioned type, they also contain the filler of 0-80% by the total mixture under the various situations except gypsum and oil chemical additive, the wetting agent of 0-2%, the softening agent of 0-5%, the promotor of 0-5%, the retarding agent of 0-5%.
Another object of the present invention is with gypsum base preparation of compositions gypsum product of the present invention.
On the one hand, above-mentioned gypsum product is the so-called prefabricated gypsum member that is widely used in building industry, comprises plasterboard, gypsum wallboard and gypsum plaster ceiling board.Relevant summary is referring to the technical chemistry macropaedia of Liv Ullmann, and the 12nd rolls up the 307th page (1976).Gypsum base composition of the present invention also can use with the form of mortar material and gypsum plaster, but gypsum plaster of especially using at the machine that further is processed into and blended gypsum plaster.At last, gypsum base composition of the present invention can also be used for the floor file mortar, and the supporting section assembly of mining based on the α gypsum, in system watt field, in metal casting and the dentistry experiment, is used as hard mould material.Relevant summary is referring to the technical chemistry macropaedia of Liv Ullmann, and the 12nd rolls up, and the 308th page, (1976).
Describe the present invention in detail by the following examples.
As the component of gypsum base composition, the setting time and the water-absorbent of following oil chemical additive are studied.
Among the preparation embodiment that is described below, with the PL gel give the system post (30 * 8.7mm), 2 * PL gel column 100A (300 * 7.8mm) and 2 * PL gel column 50A (300 * 7.8mm) carry out gel permeation chromatography experiment (GPC).Under 40 ℃, as mobile solvent, velocity of flow is the 1ml/ branch with tetrahydrofuran (THF).With the specific refractory power is that the basis is detected, and proofreaies and correct with polyoxyethylene glycol.Among the embodiment below, whatsoever all provided weight-average molecular weight (M under the situation w) and number-average molecular weight (M n).
Preferred classes under expression additive in the bracket of additive back.1 [1]2 1∶2[3]3 （ Edenol D 81，Henkel KGaA ） [3]4 1∶2.5[3]5 1∶2[1]6 1∶2[1]7 [1]8 [1]9 [1]10 [9]11 1∶1。
Product [1 class additive] 12 mol ratios are open-loop products and the phthalic acid that 1: 1 epoxidized soybean oil is used methyl alcohol
The reaction product of acid anhydride [1 class additive] 13 epoxidized soybean oils and 4-hydroxy-benzoic acid and contain 7%C 10, 48%C 12, 19
%C 16, 7%C 18, other distillatory lipid acid of 10%, Henkel KGaA's
The reaction product of product (EdenorK8-18) [1 class additive] 14 mol ratios be 1: 2 methyl epoxy stearate and the free acid of glycol reaction product [
[1 class additive] 15 epoxidation methyl stearates and ethylene oxide/propylene oxide segmented copolymer, BASF
AG(20％EO，MW＝2500g/mol)(Pluronic?PE?6200)
Free acid [1 class additive] 16 Viscotrol C of reaction product and reaction product [1 class additive] 17 mol ratios of citric acid be 2: 1 the methyl epoxy stearate and the free acid [1 of glycol reaction product
The class additive] 18 Empol 1022, a kind of is 193 based on industrial oleic acid and linoleic saponification value
The dimer (fatty acid) yl of the product of Henkel KGaA [1 class additive] preparation additive 1
Be furnished with reflux exchanger at 2 liters, in the four neck flasks of dropping funnel and water separator, the 872 fresh Viscotrol C of gram (saponification value is 193) be heated to 160 ℃.Under this temperature, in 3 hours, add 146.2 gram ditertiary butyl peroxides, and remove the trimethyl carbinol of generation by water separator then.Simultaneously, it is more and more thicker that reaction mixture becomes, and finally no longer can stir.After the cooling, obtain iodine number and be the material of 57 yellow gel sample, productive rate is 843 grams.According to GPC, M wValue is 5300, M nValue is 2542.
In 2 liters of three-necked flasks, with 77 gram 50%NaOH, 300 ml waters and 600 milliliters of alcohol reflux heating 206 restrain polymerization rapeseed oils 10 hours.Transparent reaction mixture with brown on rotary evaporator is concentrated into dried.Making the solid that obtains be dissolved in 1 premium on currency and be adjusted to pH with 10% hydrochloric acid is 1.With 800 milliliters of tetrahydrofuran (THF) aqueous phase extracted.Wash organic phase then with water up to being neutral, and at Na 2SO 4Last dry.With obtain 150 the gram polymerization rapeseed oil fatty acid (I) solution concentration, obtain brown heavy-gravity liquid, acid number is 202, iodine number is 94.According to GPC, M wValue is 904, M nValue is 698.Preparation additive 5
Under the nitrogen atmosphere, 1860 gram (2 moles) Viscotrol C and 392 are restrained (4 moles) maleic anhydrides 120 ℃ of heating.After the cooling, obtain 2200 gram products, the low viscous liquid of a kind of yellow, its acid number are 102, and iodine number is 69, and saponification value is 344.Viscosity: 8600mPas (H_ppler, 20 ℃).Preparation additive 6
Under the nitrogen atmosphere, 1860 gram (2 moles) Viscotrol C and 592 are restrained (4 moles) maleic anhydrides 120 ℃ of heating.After the cooling, obtain 2400 the gram products, the full-bodied liquid of a kind of tawny, its acid number are 93, iodine number is 64, hydroxyl value be 32 and saponification value be 318.Viscosity: 35400mPas (H_ppler, 20 ℃).Preparation additive 7
By making 100 gram dimer (fatty acid) yl 18Empol 1022, a kind of product based on industrial oleic acid and linoleic Henkel KGaA (saponification value is 193) obtains additive 7 with 10 gram magnesium hydroxide reactions.Preparation additive 8
In 2 liters of three-necked flasks of being furnished with reflux exchanger and dropping funnel, under nitrogen, 640 gram Viscotrol C (saponification value is 177,0.7 moles) are heated to 150 ℃.Under this temperature, slowly Dropwise 5 2.5 restrains the mixture that ditertiary butyl peroxides and 310 restrain Viscotrol C in 4 hours then.After temperature was reduced to 100 ℃, the trimethyl carbinol and unreacted vinylformic acid were fallen in vacuum distilling.After handling and filter with filtration adjuvant TonsilOptimum FF, obtain 900 gram products, a kind of transparent red yellow liquid, its acid number are 31, iodine number be 78 and hydroxyl value be 159.Preparation additive 9
Be similar to preparation additive 8, use 1200 gram Viscotrol C (1.26 moles), 90 gram fumaric acid (0.8 mole) and 2.6 gram ditertiary butyl peroxides make 1200 products, the thick liquid that a kind of yellow is muddy slightly, its acid number is 55, and iodine number is 72, saponification value be 229 and hydroxyl value be 146.Preparation additive 10
By making 475 gram Viscotrol C and 70 gram Vanadium Pentoxide in FLAKES reactions prepare additive 10.The acid number that characterizes this product is 161, and hydroxyl value is 66.Preparation additive 11
Be similar to additive 10, prepare additive 11 with 762 epoxidized soybean oil product and 98 gram (2.5 moles) maleic anhydrides that restrain (2.5 moles) methyl alcohol (the OH value is 184) open loops.Obtain 850 gram products, the full-bodied liquid of a kind of Vandyke brown, its acid number are 81, and saponification value is 325.Preparation additive 12
Be similar to additive 11, prepare additive 12 with 671 epoxidized soybean oil product and 358 gram (2.4 moles) Tetra hydro Phthalic anhydrides that restrain (2.2 moles) methyl alcohol (the OH value is 184) open loops.Obtain 1050 gram products, a kind of Vandyke brown solid, acid number are 58, and saponification value is 369.Preparation additive 13
155 gram (1.1 moles) 4-hydroxy-benzoic acids and 228 grams are contained 7%C 10, 48%C 12, 19%C 14, 9%C 16, 7%C 18, other distilled fatty acid of 10%, a kind of mixture of commercially available HenkelKGaA product (Edenor K 8/18) is heated to 160 ℃ under nitrogen atmosphere, added 662 gram (2.8 moles) epoxidized soybean oils (Edenor D 81) then in 3 hours.After the cooling, obtain 1030 gram reaction product, a kind of lard shape material, acid number is 40, and saponification value is 211, and hydroxyl value is 140.1.Preparation additive 14
With 53 kilograms of (156 moles) methyl epoxy stearates (Edenor MeTiO5 Epoxid, 4.71% epoxide), 19.3 kilograms of (312 moles) ethylene glycol and the 17.2 gram vitriol oils are at 100 ℃, and heating is about 1 hour under the nitrogen atmosphere.Then under this temperature with 10 grams, 30% sodium methoxide solution neutralization reaction mixture, by temperature being elevated to 200 ℃, and part is distilled in vacuum (2 torr).Behind the cool to room temperature, add the solution of 13.5 kilograms of 50%NaOH (169 moles) in 20 kg water, then stirred 1 hour down at 80-100 ℃.After adding 250 milliliter of 13% chlorine bleach liquor, under 70 ℃, with 23.6 kilogram of 35% sulfuric acid neutralization reaction mixture.Remove water, water repetitive scrubbing residue and vacuum-drying.Obtain 46 kilograms of products, a kind of light brown thick liquid, its acid number are 157, and iodine number is 10, saponification value be 162 and hydroxyl value be 253.Preparation additive 15
Be similar to the preparation method of additive 14, with 398 gram (1.2 moles) methyl epoxy stearate (EdenorMeTiO 5Epoxid, 4.71% epoxide) and 1025 gram (0.4 mole) 1 prepare additive 15.Obtain about 1200 the gram products, a kind of deep yellow, solid/liquid material, its acid number are 53, saponification value be 58 and hydroxyl value be 52.Preparation additive 16
Under 180 ℃ of nitrogen atmosphere, in water separator, 1032 gram (1 mole) Viscotrol C and 187 gram (1 mole) Citric Acid, usp, Anhydrous Powders were heated about 2 hours.After the cooling, obtain 1135 the gram products, a kind of yellow thick liquid, its acid number are 70, iodine number is 73, saponification value be 292 and hydroxyl value be 134.Preparation additive 17
Be similar to the preparation method of additive 14, with 60 kilograms of (177 moles) methyl epoxy stearate (Edenor MeTiO 5Epoxid, 4.71% epoxide) and 5.5 kilograms of (88.5 moles) 1 prepare additive 17.Obtain about 60 kilograms of products, a kind of yellow thick liquid, its acid number are 177, saponification value be 180 and hydroxyl value be 140.
Measure solidification rate and water-absorbent as follows:
Oil chemical additive is joined in 70 ml waters.Under vigorous stirring, add 140 gram gypsum (CaSO then 4H 2O) (Alfor, B_rgardts-Sachsenstein; Density is 2.63, and apparent density is 900 grams per liters).When mixture was even, it was in 85 millimeters the aluminium dish that test block is cast in diameter, measures the setting rate of test block.After storing 48 hours, on the pit of test block, pour 10 ml waters into, measure water-absorbent and measure and permeate fully the required time (minute).The percentage of shown additive is based on the percentage of total water/gypsum mixtures (210 gram).In this experiment, it should be noted that when penetration time is several hours (as situation possible in the additive 1) that a large amount of water are evaporated.
Listed experimental result in the following table.All oil chemical additives use as hydrophobizing agent in some cases as solidifying retarding agent.The additive concentration setting time water-absorbent time
% (weight) (minute) (minute)
0 14 2.08 1 0.25 26 2.63 1 0.5 24 2.93 1 0.75 28 3.05 1 1 29 3.42 1 2.5 30 13.85 1 5 35 496.00 1 10 35 86.00 2 0.1 21 3.15 2 0.25 25 3.15 2 0.5 27 3.30 2 0.75 32 4.20 2 1.32 27 5.45 2 4.76 45 18.45 2 9.1 ＞300 26.15 3 4.76 38 5.30 4 4.76 ＞240 5 5.00 960 6 5.00 22 1.98 7 5.00 24 15.33 8 5.00 65 1.73 9 5 70 1.80 10 5 106 1.97 11 5 960 12 5 20 1.90 13 5 26 5.03 14 5 960 15 5 960 16 5 133 2.50 17 5 36 9.00 18 5 25 14.00

Claims (25)

1. a gypsum base composition is characterized in that, contains at least a oil chemical additive that is selected from following compounds of 0.1-30% weight by the dry mixture total amount
--at least a molecular weight is 143-20000's and contain at least one carboxyl and have the fatty cpd of 8 carbon atoms at least, and/or their salt;
--at least a molecular weight is 130-20000's and contain at least one hydroxyl and have the fatty cpd of 8 carbon atoms at least;
--at least a molecular weight is 158-20000's and contain the fatty cpd of at least one ester group, and its acid constituents and/or alkoxide component contain at least 8 carbon atoms;
--at least a molecular weight is 144-20000's and contain the fatty cpd of at least one ether, and at least one group in two ether contains at least 8 carbon atoms;
--at least a molecular weight is 129-20000 and contains at least one fatty cpd amino or at least one quaternary ammonium salt, wherein, is arranged in around the nitrogen-atoms three or four at least one groups wherein and contains at least 8 carbon atoms;
--at least a molecular weight is 157-20000 and the fatty cpd that contains at least one amide group, and wherein the acid moieties of acid amides contains at least 8 carbon atoms;
--at least a molecular weight is 128-20000 and contains at least one epoxide group and the fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight is 210-20000 and contains at least one anhydride group and the fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight is 193-20000 and contains the organophosphorus fat compound that has 8 carbon atoms at least;
--at least a molecular weight is 174-20000 and contains the organic boron fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight is 164-20000 and contains the organosulfur fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight is 213-20000 and contains at least one urethane group and the fatty cpd that has 8 carbon atoms at least; And/or
--at least a molecular weight is 130-20000 and contains at least one ketone groups and the fatty cpd that has 8 carbon atoms at least;
--its condition is not use higher fatty acid or its salt as at least a fatty cpd that contains at least one carboxyl separately, another condition is, do not use Fatty Alcohol(C12-C14 and C12-C18) or ethoxylized fatty alcohol as at least a fatty cpd that contains at least one hydroxyl separately, another condition is not use natural fat or oil as at least a fatty cpd that contains at least one ester group separately;
--its condition is not use C separately 10-16The sulphonate of fatty acid alkyl ester as the organosulfur fatty cpd and
--its condition is not use the ethylene oxide adduct of fatty acid amide as a kind of fatty cpd that contains at least one amide group at least separately;
Wherein the consumption of gypsum is counted 20-99.9% weight by amount of the mixture.
2. according to the composition of claim 1, it is characterized in that, contain 0.5-15% weight by the dry mixture total amount.
3. according to the composition of claim 1 or 2, it is characterized in that, contain the fatty cpd of at least one carboxyl, also contain ester group at least one hydroxyl and Fei Bi ground or ether.
4. according to the composition of claim 1 or 2, it is characterized in that, contain the fatty cpd of at least one carboxyl, also contain at least one ester group and optionally at least one ether or at least one anhydride group.
5. according to the composition of claim 1 or 2, it is characterized in that, contain the fatty cpd of at least one carboxyl, also contain an anhydride group.
6. according to the composition of claim 1 or 2, it is characterized in that, the fatty cpd that contains at least one hydroxyl also contains at least one ester group and optionally at least one is selected from least one amido, other group of at least one amide group and at least one anhydride group.
7. according to the composition of claim 1 or 2, it is characterized in that, contain the fatty cpd of at least one hydroxyl, also contain other group that at least one is selected from least one ether and at least one amide group.
8. according to the composition of claim 1 or 2, it is characterized in that, contain the fatty cpd of at least one ester group, also contain at least one and be selected from least one amide group, other group of at least one epoxide group or at least one anhydride group.
9. according to the composition of claim 1 or 2, it is characterized in that, contain the fatty cpd of at least one ester group, also contain at least one epoxide group and at least one ether.
10. according to the composition of claim 1 or 2, it is characterized in that, contain at least one fatty cpd amino or at least one quaternary ammonium compound, also contain at least one amide group.
11. the composition according to claim 1 or 2 is characterized in that, organophosphorus fat compound contains the ester of phosphoric acid or phosphorous acid.
12. the composition according to claim 1 or 2 is characterized in that, organic boron fatty cpd contains the boric acid fatty ester.
13. the composition according to claim 1 or 2 is characterized in that, the organosulfur fatty cpd contains the ester of sulfuric acid or sulfurous acid or contains the fatty cpd and the chlorsulfonic acid of activating group, the reaction product of sulphur trioxide or oleum.
14. the composition according to claim 1 or 2 is characterized in that, contains the fatty cpd of at least one urethane group, also contains the fatty cpd of hydroxyl and simple function and/or polyfunctional isocyanate's reaction product.
15. the composition according to aforesaid right requires is characterized in that, contains the siccative of 0.01-1% weight by fatty cpd.
16. the composition according to aforesaid right requires is characterized in that gypseous composition contains a kind of with the plaster of paris, the gypsum that synthetic gypsum or waste-gas desulfurization produce is the gypsum on basis.
17. the composition according to aforesaid right requires is characterized in that, also contains the filler of 0-80% weight, 0-2% weight moistening agent, 0-5% weight softening agent, 0-5% weight promotor, 0-5% weight retarding agent by amount of the mixture.
18. the purposes of gypsum base composition among the claim 1-17, it is used to prepare gypsum product.
19. the purposes according to claim 18 is characterized in that, gypsum product is the gypsum member.
20., it is characterized in that gypsum product is a gypsum plaster according to the purposes of claim 18.
21., it is characterized in that gypsum product is that gypsum is scraped slurry according to the purposes of claim 18.
22. the purposes of the gypsum base composition of claim 1-16 is used to prepare mortar mix.
23. the purposes of the gypsum base composition of claim 1-17 is used to prepare the gypsum base assembling and sticks with glue agent.
24. the purposes of the gypsum base composition of claim 1-16 is used to prepare the model composition.
25. the purposes of oil chemical additive is used to handle gypsum member and gypsum plaster, described additive comprises
--at least a molecular weight is 143-20000 and contains at least one carboxyl and the fatty cpd that has 8 carbon atoms at least, and/or their salt;
--at least a molecular weight is 130-20000 and contains at least one hydroxyl and the fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight is 158-20000's and contain the fatty cpd of at least one ester group, and its acid constituents and/or alkoxide component contain at least 8 carbon atoms;
--at least a molecular weight is 144-20000's and contain the fatty cpd of at least one ether, and at least one group in two ether contains at least 8 carbon atoms;
--at least a molecular weight is 129-20000 and contains at least one fatty cpd amino or at least one quaternary ammonium salt, wherein, is arranged at least one group in around the nitrogen-atoms three or four bases and contains and have 8 carbon atoms at least;
--at least a molecular weight is 157-20000 and the fatty cpd that contains at least one amide group, and wherein the acid moieties of acid amides contains at least 8 carbon atoms;
--at least a molecular weight is 128-20000 and contains at least one epoxide group and the fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight is 210-20000 and contains at least one anhydride group and the fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight is 193-20000 and contains the organophosphorus fat compound that has 8 carbon atoms at least;
--at least a molecular weight is 174-20000 and contains the organic boron fatty cpd that has 8 carbon atoms at least;
--at least a thing molecular weight is 164-20000 and contains the organosulfur fatty cpd that has 8 carbon atoms at least;
--at least a molecular weight be 213-20000 and contain at least one urethane group and have at least 8 carbon atoms fatty cpd and/or
--at least a molecular weight is 130-20000 and contains at least one ketone groups and the fatty cpd that has 8 carbon atoms at least;
--its condition has the fatty cpd of 10 carbon atoms as at least a fatty cpd that contains at least one carboxyl for not using separately.
CN96196130A 1995-08-23 1996-08-14 Gypsum-contg. composition and its use Expired - Fee Related CN1097036C (en)

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DE102005051589A1 (en) * 2005-10-27 2007-05-03 Wacker Polymer Systems Gmbh & Co. Kg Fatty acid anhydrides containing dispersion powder
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